CN101489926A - Carbon nanowall with controlled structure and method for controlling carbon nanowall structure - Google Patents
Carbon nanowall with controlled structure and method for controlling carbon nanowall structure Download PDFInfo
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- CN101489926A CN101489926A CNA2007800263113A CN200780026311A CN101489926A CN 101489926 A CN101489926 A CN 101489926A CN A2007800263113 A CNA2007800263113 A CN A2007800263113A CN 200780026311 A CN200780026311 A CN 200780026311A CN 101489926 A CN101489926 A CN 101489926A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 106
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 238000001237 Raman spectrum Methods 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims description 79
- 230000008676 import Effects 0.000 claims description 53
- 239000003054 catalyst Substances 0.000 claims description 20
- 238000001228 spectrum Methods 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000000446 fuel Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 150000001721 carbon Chemical class 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 6
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 210000002381 plasma Anatomy 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000002717 carbon nanostructure Substances 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 239000003273 ketjen black Substances 0.000 description 3
- 239000002060 nanoflake Substances 0.000 description 3
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 241001584775 Tunga penetrans Species 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 241000220317 Rosa Species 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/18—Nanoonions; Nanoscrolls; Nanohorns; Nanocones; Nanowalls
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
Abstract
The invention provides a method of controlling the structure of carbon nanowall (CNW) in which the interwall spacing of carbon nanowall (CNW) is varied so as to control the surface area thereof or control the crystallinity thereof, thereby enhancing the corrosion resistance at high potential; and a highly crystalline carbon nanowall (CNW) and carbon nanowall (CNW) of large surface area with controlled structure. There are provided (1) carbon nanowall characterized by having a wall surface area of 50 cm<2>/cm<2>-substrate mum or greater, (2) carbon nanowall characterized by having a crystallinity such that the D-band half value width of Raman spectrum measured with an irradiation laser wavelength of 514.5 nm is 85 cm<-1> or less; and (3) carbon nanowall characterized by having not only a wall surface area of 50 cm<2>/cm<2>-substrate mum or greater but also a crystallinity such that the D-band half value width of Raman spectrum measured with an irradiation laser wavelength of 514.5 nm is 85 cm<-1> or less.
Description
Technical field
The present invention relates to the structure control method of carbon nanometer wall, relate to the controlled novel carbon nanometer wall of structure of the surface-area that obtains by this method and crystallinity etc. simultaneously.
Background technology
As the carbon with nano-scale structure is porous material, and it is porous material that graphite and unbodied carbon are arranged, for example known soccerballene, carbon nanotube, carbon nanometer loudspeaker, carbon nano flake etc.
At the carbon with nano-scale structure is in the porous material, and carbon nanometer wall (CNW) is the carbon nano structure with two-dimensional expansion, and typical case is the carbon nanometer wall with the wall shape structure that erects with roughly certain direction from the surface of base material.Soccerballene (C60 etc.) is the carbon nano structure of zero dimension, and carbon nanotube can be regarded the unidimensional carbon nano structure as.In addition, the carbon nano flake is the plane small pieces aggregate with two-dimensional expansion that is similar to carbon nanometer wall, but is that small pieces do not interconnect one by one as the rose petal, and is inferior to the carbon nano structure of carbon nanometer wall with respect to the orientation of substrate.Therefore, carbon nanometer wall is the carbon nano structure that has with soccerballene, carbon nanotube, carbon nanometer loudspeaker, the diverse feature of carbon nano flake.
Present inventors are conceived to carbon nanometer wall, and are open in TOHKEMY 2005-97113 communique for its manufacture method and manufacturing installation.Particularly as shown in Figure 7, will be that the unstripped gas 32 that constitutes element imports in the reaction chamber 10 at least with carbon.In this reaction chamber 10, be provided with parallel plate-type capacitance coupling plasma (CCP) generating mechanism 20 that comprises first electrode 22 and second electrode 24.Thus, the hertzian wave of irradiation RF ripple etc., unstripped gas 32 form plasmas plasma atmosphere 34.On the other hand, in the free radical generation chamber 41 of the outside that is arranged at reaction chamber 10, utilize decomposition such as RF ripple to contain the radical source gas 36 of hydrogen at least, generate hydroperoxyl radical 38.This hydroperoxyl radical 38 is injected plasma atmosphere 34, form carbon nanometer wall on the surface that is disposed at the substrate 15 on second electrode 24.
Summary of the invention
The existence of known good several carbon nanometer walls (CNW) and basic generation method thereof, but be used to make the shape transitivity of carbon nanometer wall (CNW) meet its use, form the structure control method of best carbon nanometer wall, it be not immediately clear.
Therefore, the objective of the invention is, interval variation between the wall that makes carbon nanometer wall (CNW) is provided, control its surface-area, control its crystallinity, the structure control method of the carbon nanometer wall (CNW) of the erosion resistance of raising under noble potential provides simultaneously through the carbon nanometer wall (CNW) of the high surface area of structure control and the carbon nanometer wall (CNW) of high crystalline.
Present inventors find, the import volume ratio that generates the process gas in the technology by the carbon nanometer wall (CNW) that makes plasma CVD changes, interval between the wall of carbon nanometer wall (CNW) is changed, can control the structure of its surface-area and crystallinity etc., thereby finish the present invention.
That is, the 1st, the present invention is the invention of having controlled the carbon nanometer wall of the structure of shape and rerum natura etc., is following (1)～(3).
(1) a kind of wall surface is long-pending is 50cm
2/ cm
2The carbon nanometer wall of the high surface area that-substrate μ m is above.(at this, wall surface is long-pending to be that the wall surface of per unit substrate area, per unit wall height is long-pending.) for example, the electrode catalyst agent carrier that the battery that acts as a fuel is used uses the occasion of carbon nanometer wall, when its surface-area was big, therefore the increase of catalyst loading amount was preferred, preferred wall surface is long-pending to be 50cm
2/ cm
2The carbon nanometer wall that-substrate μ m is above, more preferably wall surface is long-pending is 60cm
2/ cm
2The carbon nanometer wall that-substrate μ m is above, further preferred wall surface is long-pending to be 70cm
2/ cm
2The carbon nanometer wall that-substrate μ m is above.
(2) a kind of wide 85cm of being of D bands of a spectrum half value with Raman spectrum of measuring with irradiating laser wavelength 514.5nm
-1Following crystalline carbon nanometer wall.For example, use the occasion of carbon nanometer wall as the electronic material of paying attention to the electroconductibility size, the high person's electroconductibility of its crystallinity height, therefore the excellent corrosion resistance under noble potential simultaneously has preferably that the D bands of a spectrum half value of Raman spectrum is wide to be 85cm
-1Following crystalline carbon nanometer wall has more preferably that the D bands of a spectrum half value of Raman spectrum is wide to be 65cm
-1Following crystalline carbon nanometer wall has preferably further that the D bands of a spectrum half value of Raman spectrum is wide to be 50cm
-1Following crystalline carbon nanometer wall.
(3) a kind of carbon nanometer wall that has high surface area and high crystalline simultaneously, its wall surface is long-pending to be 50cm
2/ cm
2More than-substrate μ the m, has the wide 85cm of being of D bands of a spectrum half value of the Raman spectrum of measuring with irradiating laser wavelength 514.5nm simultaneously
-1Following crystallinity.This carbon nanometer wall, because its surface-area is big, so the increase of catalyst loading amount, simultaneously owing to its crystallinity height, so electroconductibility is high and the excellent corrosion resistance under noble potential, and the electrode catalyst agent carrier that the battery that particularly acts as a fuel is used is optimum.
The 2nd, the present invention is the invention of having controlled the structure control method of the carbon nanometer wall of structural shapes such as surface-area and crystallinity and rerum natura, formation will be to constitute the plasma atmosphere that the carbon-source gas plasma of element forms at least with carbon at least a portion of reaction chamber, be infused in the outside of this atmosphere by H in this plasma atmosphere simultaneously
2The hydroperoxyl radical that gas generates reacts both, and the surface of the base material in being disposed at this reaction chamber forms in the carbon nanometer wall manufacture method of carbon nanometer wall, with this H
2The import volume of gas and this carbon-source gas likens to setting the factor and controls the surface-area and/or the crystallinity of the carbon nanometer wall of generation.
Moreover the absolute value that wall surface is long-pending is except depending in the present invention as the H that sets the factor
2The import volume of gas and carbon-source gas is than (H
2Gas import volume (mol)/carbon-source gas import volume (mol)) in addition, also set the value decision of the factor by other, but in this manual, set the factor about these other, substrate temperature is made as 970 ℃, cavity indoor pressure is made as that 800mTorr, substrate material are made as silicon, plasma generating source output is made as 13.56MHz, 100W, thereby its import volume ratio is discussed.
At this, as the H that sets the factor
2The import volume of gas and carbon-source gas is than (H
2Gas import volume (mol)/carbon-source gas import volume (mol)), can in the scope of broad, change according to the shape and the rerum natura of the surface-area of desirable carbon nanometer wall and crystallinity etc.Usually, can make H
2The import volume of gas and carbon-source gas is than (H
2Gas import volume (mol)/carbon-source gas import volume (mol)) is changed to about 0.5～3, but is being to form carbon nanometer wall under 1～2.5 the situation in the practicality.
Specifically, by with H
2The import volume of gas and carbon-source gas is than (H
2Gas import volume (mol)/carbon-source gas import volume (mol)) is decided to be below 1.8, can forms the long-pending 50cm of being of wall surface
2/ cm
2The carbon nanometer wall that-substrate μ m is above.By with H
2The import volume of gas and carbon-source gas is than (H
2Gas import volume (mol)/carbon-source gas import volume (mol)) is decided to be below 1.4, can forms the long-pending 60cm of being of wall surface
2/ cm
2The carbon nanometer wall that-substrate μ m is above is by with H
2The import volume of gas and carbon-source gas is than (H
2Gas import volume (mol)/carbon-source gas import volume (mol)) is decided to be below 1.0, can forms the long-pending 70cm of being of wall surface
2/ cm
2The carbon nanometer wall that-substrate μ m is above.
In addition, by making H
2The gas import volume is 2.5sccm/cm
2More than-parallel plate electrode the area, can form the wide 85cm of being of the D bands of a spectrum half value with Raman spectrum
-1The carbon nanometer wall of following high crystalline is by making H
2The gas import volume is 4.2sccm/cm
2More than-parallel plate electrode the area, can form the wide 65cm of being of the D bands of a spectrum half value with Raman spectrum
-1The carbon nanometer wall of following high crystalline is by making H
2The gas import volume is 5.8sccm/cm
2More than-parallel plate electrode the area, can form the wide 50cm of being of the D bands of a spectrum half value with Raman spectrum
-1The carbon nanometer wall of following high crystalline.
In the present invention, for by H
2Gas generates hydroperoxyl radical, for example can list to H
2Gas irradiation be selected from microwave, UHF ripple, VHF ripple and the RF ripple more than one ripple method, make H
2The method that gas contacts with the catalyst metal that has been heated.
In the present invention, as the initial substance that becomes carbon-source gas, can enumerate at least with carbon and hydrogen as the compound that constitutes element, at least with carbon and fluorine as the compound that constitutes element.
The 3rd, the present invention is a kind of catalyst for fuel cell layer, it is characterized in that, the catalyst layer carrier is the above-mentioned carbon nanometer wall through structure control, the catalyzer that forms by this carbon nanometer wall with carrier on, support and be dispersed with catalyst component and/or electrolyte ingredient.By use the carbon nanometer wall have high surface area and high crystalline simultaneously to act as a fuel electrode catalyst agent carrier that battery uses, because its surface-area is big, therefore the catalyst loading amount increases, simultaneously because its crystallinity height, so electroconductibility is high and the excellent corrosion resistance under noble potential, and the electrode catalyst agent carrier that the battery that particularly acts as a fuel is used is excellent.
The import volume ratio that generates the process gas in the technology by the carbon nanometer wall (CNW) that makes plasma CVD changes, and the interval between the wall of carbon nanometer wall (CNW) is changed, and can control its surface-area, can control its crystallinity.Carbon nanometer wall of the present invention, because its surface-area is big, the catalyst loading amount increases, simultaneously owing to its crystallinity height, the high and excellent corrosion resistance under noble potential of electroconductibility, the electrode catalyst agent carrier that the battery that particularly acts as a fuel is used is only.
Description of drawings
Fig. 1 is the mode chart of an example that is used to form the device of the carbon nanometer wall through structure control of the present invention.
Fig. 2 is the mode chart of the device that is used to form carbon nanometer wall that uses in an embodiment.
Fig. 3 represents hydrogen (H
2) and carbon-source gas (C
2F
6) import volume than, with the long-pending relation of wall surface of the carbon nanometer wall of growth.
Fig. 4 represents H
2Import volume/C
2F
6The surperficial SEM photo picture of the carbon nanometer wall under the situation of import volume=2.
Fig. 5 represents H
2Import volume/C
2F
6The surperficial SEM photo picture of the carbon nanometer wall under the situation of import volume=1.
Fig. 6 represents hydrogen (H
2) the crystalline relation of import volume and the carbon nanometer wall of trying to achieve by Raman spectrum analysis.
Fig. 7 represents an example of the control device of carbon nanometer wall.
Label among the figure is as follows:
1: plasma CVD apparatus; 2: silicon (Si) substrate; 3: the well heater in the chamber; 4: the plate electrode parallel with substrate 2; 5: the carbon-source gas ingress pipe; 6: hydrogen (H
2) ingress pipe; 7: plasma generating source; 8: the plasma generating source of induction type; 9: the high frequency take-off equipment; 10: reaction chamber; 15: the carbon-source gas ingress pipe; 20: plasma cell; 22: the first electrodes; 24: the second electrodes; 32: unstripped gas (raw material); 34: plasma atmosphere; 36: radical source gas (free radical source matter); 38: free radical; 41: the free radical generation chamber
Embodiment
Fig. 1 is the mode chart of an example that is used to form the device of the carbon nanometer wall through structure control of the present invention.Between the parallel plate electrode in chamber shown in Figure 1, except CF
4, C
2F
6Or CH
4Etc. carbonaceous reactant gases (carbon-source gas) in addition, also import hydroperoxyl radical, form carbon nanometer wall by PECVD (Plasma Enhanced Chemical Vapor Deposition (PECVD)).At this moment, substrate preferably is heated to about more than 500 ℃.In addition, the distance of parallel plate electrode is about 5cm, at the high frequency take-off equipment generation condenser coupling type plasma of dull and stereotyped chien shih with for example 13.56MHz, output rating 100W.In addition, it is the silica tube of for example long 200mm, internal diameter Φ 26mm that hydroperoxyl radical generates the position, imports H
2Gas uses the high frequency take-off equipment of 13.56MHz, output rating 400W to produce jigger coupling type plasma.Suitable change carbon-source gas and H
2The flow of gas, cavity indoor pressure is for example 100mTorr.But this device is an example only, does not limit experiment condition, equipment and result according to this paper.
Use plasma CVD apparatus shown in Figure 2, and will be arranged on by the substrate 2 that silicon (Si) forms on the well heater 3 in the chamber, between the plate electrode 4 parallel, import carbon-source gas (C with substrate 2 from ingress pipe 5
2F
6), import hydrogen (H from other ingress pipe 6 simultaneously
2).At this moment, the temperature of well heater 3 is set in 970 ℃.
Distance between plate electrode 4 and the substrate 2 is made as 5cm, and the electricity of plasma generating source 7 is output as 13.56MHz, 100W, makes the plasma that the condenser coupling type takes place between plate electrode 4 and the substrate 2.In addition, the plasma generating source 8 by induction type makes the plasma that the jigger coupling type takes place in the ingress pipe 6.At this moment, high frequency take-off equipment 9 is output as 13.56Hz, 400W.The area of parallel plate electrode is 19.625cm
2(Φ 50mm).
The plasma CVD method of employing under above-mentioned condition grown carbon nanometer wall (CNW) on substrate 2.The flow of carbon-source gas is made as 50sccm, and the flow of hydrogen is divided into 50sccm (H
2Gas import volume (mol)/carbon-source gas import volume (mol)=1), 70sccm (H
2Gas import volume (mol)/carbon-source gas import volume (mol)=1.4), 100sccm (H
2Gas import volume (mol)/carbon-source gas import volume (mol)=2), 125sccm (H
2Gas import volume (mol)/carbon-source gas import volume (mol)=2.5) these 4 levels are grown.
At this moment, the pressure in the chamber is made as 800mTorr.The height of carbon nanometer wall that has carried out 30 minutes growth in this system is about 300～750nm, and the thickness of wall is 10～50nm.
Fig. 3 represents hydrogen (H
2) and carbon-source gas (C
2F
6) import volume than, with the long-pending relation of wall surface of the carbon nanometer wall of growth.In addition, Fig. 4 represents H
2Import volume/C
2F
6The surperficial SEM photo picture of the carbon nanometer wall under the situation of import volume=2, Fig. 5 represents H
2Import volume/C
2F
6The surperficial SEM photo picture of the carbon nanometer wall under the situation of import volume=1.
Result by Fig. 3～Fig. 5 knows, H
2The import volume of gas and carbon-source gas is than (H
2Gas import volume (mol)/carbon-source gas import volume (mol)) more little, the interval of wall is more little, and surface-area is big more.
Real example in CVD technology similarly to Example 1, by making H
2The import volume of gas changes, and also can control its crystallinity independently.
Fig. 6 represents H
2The crystalline relation of import volume and the carbon nanometer wall of trying to achieve by Raman spectrum analysis.Crystalline height is that the D bands of a spectrum half value of the Raman spectrum that will measure with irradiating laser wavelength 514.5nm is wide to be inferred as index.D bands of a spectrum half value is wide more little, and crystallinity is high more.That is, by reducing H
2Import volume can improve the crystallinity of carbon nanometer wall.In Fig. 6,, added wide and D bands of a spectrum half value graphite is wide as the D bands of a spectrum half value of the Ketjen black (Ketjenblack) of in the past carrier for reference.Even carbon nanometer wall also can access the high crystalline more than Ketjen black as can be known.
Utilize possibility on the industry
Carbon nanometer wall of the present invention, because its surface area is big, so the increase of catalyst loading amount, simultaneously Because its crystallinity height, so electric conductivity is high and the excellent corrosion resistance under high potential, particularly does For the electrode catalyst agent carrier that fuel cell is used optimum. Thus, practical and general to fuel cell And contribute.
Among the present invention the expression number range " more than " and " following " include given figure.
Claims (9)
1. a carbon nanometer wall is characterized in that, wall surface is long-pending to be 50cm
2/ cm
2More than-substrate μ the m.
2. a carbon nanometer wall is characterized in that, has the wide 85cm of being of D bands of a spectrum half value of the Raman spectrum of measuring with irradiating laser wavelength 514.5nm
-1Following crystallinity.
3. a carbon nanometer wall is characterized in that, wall surface is long-pending to be 50cm
2/ cm
2More than-substrate μ the m, has the wide 85cm of being of D bands of a spectrum half value of the Raman spectrum of measuring with irradiating laser wavelength 514.5nm simultaneously
-1Following crystallinity.
4. the structure control method of a carbon nanometer wall, it is characterized in that, formation will be to constitute the plasma atmosphere that the carbon-source gas plasma of element forms at least with carbon at least a portion of reaction chamber, be infused in the outside of this atmosphere by H in this plasma atmosphere simultaneously
2The hydroperoxyl radical that gas generates reacts both, and the surface of the base material in being disposed at this reaction chamber forms in the carbon nanometer wall manufacture method of carbon nanometer wall, with this H
2The import volume of gas and this carbon-source gas likens to setting the factor and controls the surface-area and/or the crystallinity of the carbon nanometer wall of generation.
5. the structure control method of carbon nanometer wall according to claim 4 is characterized in that, described H
2The import volume ratio of gas and carbon-source gas, i.e. H
2It is 1～2.5 that gas imports molar weight/carbon-source gas importing molar weight.
6. according to the structure control method of claim 4 or 5 described carbon nanometer walls, it is characterized in that, by to described H
2Gas irradiation be selected from microwave, UHF ripple, VHF ripple and the RF ripple more than one ripple and/or make H
2Gas contacts with the catalyst metal that has been heated, by H
2Gas generates hydroperoxyl radical.
7. according to the structure control method of each described carbon nanometer wall of claim 4～6, it is characterized in that, described carbon-source gas to major general's carbon and hydrogen as constituting element.
8. according to the structure control method of each described carbon nanometer wall of claim 4～6, it is characterized in that, described carbon-source gas to major general's carbon and fluorine as constituting element.
9. catalyst for fuel cell layer, it is characterized in that, the catalyst layer carrier is each described carbon nanometer wall of claim 1～3, supports and be dispersed with catalyst component and/or electrolyte ingredient at the catalyst layer that is formed by this carbon nanometer wall on carrier.
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| JP2006201927A JP4662067B2 (en) | 2006-07-25 | 2006-07-25 | Structure-controlled carbon nanowall and structure control method of carbon nanowall |
| JP201927/2006 | 2006-07-25 | ||
| PCT/JP2007/065036 WO2008013309A1 (en) | 2006-07-25 | 2007-07-25 | Carbon nanowall with controlled structure and method of controlling structure of carbon nanowall |
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| EP (1) | EP2048113B1 (en) |
| JP (1) | JP4662067B2 (en) |
| CN (1) | CN101489926B (en) |
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| WO (1) | WO2008013309A1 (en) |
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-
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-
2007
- 2007-07-25 WO PCT/JP2007/065036 patent/WO2008013309A1/en active Application Filing
- 2007-07-25 CA CA2654430A patent/CA2654430C/en not_active Expired - Fee Related
- 2007-07-25 US US12/374,844 patent/US20100009242A1/en not_active Abandoned
- 2007-07-25 CN CN2007800263113A patent/CN101489926B/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| US20100009242A1 (en) | 2010-01-14 |
| WO2008013309A1 (en) | 2008-01-31 |
| JP4662067B2 (en) | 2011-03-30 |
| CA2654430C (en) | 2011-12-13 |
| CA2654430A1 (en) | 2008-01-31 |
| EP2048113A1 (en) | 2009-04-15 |
| EP2048113B1 (en) | 2014-02-26 |
| JP2008024570A (en) | 2008-02-07 |
| CN101489926B (en) | 2013-05-15 |
| EP2048113A4 (en) | 2010-03-17 |
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